WO2021199339A1 - Adhésif thermofusible réactif, corps lié et son procédé de production, et vêtement - Google Patents

Adhésif thermofusible réactif, corps lié et son procédé de production, et vêtement Download PDF

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Publication number
WO2021199339A1
WO2021199339A1 PCT/JP2020/014927 JP2020014927W WO2021199339A1 WO 2021199339 A1 WO2021199339 A1 WO 2021199339A1 JP 2020014927 W JP2020014927 W JP 2020014927W WO 2021199339 A1 WO2021199339 A1 WO 2021199339A1
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Prior art keywords
reactive hot
hot melt
adhesive
urethane prepolymer
melt adhesive
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PCT/JP2020/014927
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English (en)
Japanese (ja)
Inventor
和樹 久野
淑杰 曲
翔太 青柳
琢磨 鈴木
聡一郎 小宮
和幸 馬籠
卓也 今井
淳一 亀井
晃一 斉藤
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昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to JP2022511403A priority Critical patent/JPWO2021199339A1/ja
Priority to PCT/JP2020/014927 priority patent/WO2021199339A1/fr
Priority to CN202080099156.3A priority patent/CN115335568A/zh
Publication of WO2021199339A1 publication Critical patent/WO2021199339A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M17/00—Producing multi-layer textile fabrics
    • D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
    • D06M17/10—Polyurethanes polyurea

Definitions

  • the present disclosure relates to reactive hot melt adhesives, adhesives and methods for producing them, and clothing.
  • Hot melt adhesive is a solvent-free adhesive, it has less impact on the environment and the human body, and it can be adhered for a short time, so it is suitable for improving productivity.
  • Hot melt adhesives can be broadly divided into two types: those containing a thermoplastic resin as a main component and those containing a reactive resin as a main component.
  • a reactive resin a urethane prepolymer having an isocyanate group at the end is mainly used.
  • the reactive hot melt adhesive containing urethane prepolymer as the main component develops a certain degree of adhesive strength in a short time by cooling and solidifying the adhesive itself after application. After that, the terminal isocyanate group of the urethane prepolymer reacts with moisture (moisture in the air or on the surface of the adherend) to increase the molecular weight, and crosslinks occur to develop heat resistance.
  • moisture moisture in the air or on the surface of the adherend
  • crosslinks occur to develop heat resistance.
  • Such an adhesive is called a moisture-curable reactive hot melt adhesive.
  • Reactive hot melt adhesives containing urethane prepolymer as the main component show good adhesive strength even when heated.
  • Patent Document 1 describes a polyol (b) composed of a polyisocyanate (a), an aromatic ring-containing polyether polyol (b1) and / or an aromatic ring-containing polyester polyol (b2), and an aliphatic polyester polyol (b3).
  • Reactive hot melt adhesives made of urethane prepolymers formed from are disclosed.
  • the main object of the present disclosure is to provide a reactive hot melt adhesive having excellent adhesive strength and excellent elasticity.
  • the present inventors conducted a 13- C-NMR analysis on the urethane prepolymer and investigated the structural units contained in the urethane prepolymer. As a result, the integrated value of the peaks observed in a predetermined range was predetermined. It has been found that the urethane prepolymer having a ratio of 1) tends to have excellent adhesive strength and elasticity, and has completed the invention of the present disclosure.
  • the reactive hot melt adhesive contains a urethane prepolymer.
  • C (A) the integral value of the peak observed in the range of 163 to 170 ppm
  • C (B) the integral value of the peak observed in the range of 171 to 176 ppm
  • C (A) and C (B) satisfy the following formula (X).
  • Such a reactive hot melt adhesive has excellent adhesive strength and elasticity. 0.36 ⁇ C (A) / (C (A) + C (B)) (X)
  • the integrated value for example, it is possible to measure the integrated value for each peak observed in the range of 163 to 170 ppm and set the sum of the integrated values as C (A), but the integrated value is used. Since it is easy to obtain and the arbitrariness can be reduced, the integrated value of the entire range of 163 to 170 ppm can be measured collectively and the integrated value can be designated as C (A) (see, for example, FIGS. 2 and 3). ). The same applies to C (B) and C (C).
  • the integral value of the peak observed in the range of 163 to 170 ppm, the integral value of the peak observed in the range of 171 to 176 ppm, and the integral value of the peak observed in the range of 150 to 155 ppm are 163 to 170 ppm, respectively.
  • the urethane prepolymer may be, for example, a urethane prepolymer having an isocyanate group.
  • a urethane prepolymer having an isocyanate group usually has a polymer chain containing a structural unit derived from a polyol and a structural unit derived from polyisocyanate, and an isocyanate group.
  • the isocyanate group may be bonded to the end of the polymerized chain. 13
  • the peak observed in the range of 160 to 180 ppm is mainly the structural unit derived from the polyol constituting the urethane prepolymer, and the carbonyl group of the ester bond of the structural unit derived from the polyester polyol.
  • the peak observed in the range of 163 to 170 ppm is the carbon atom of the carbonyl group directly bonded to the carbon atom constituting the aromatic ring among the carbon atoms of the carbonyl group of the ester bond of the polyester polyol (hereinafter, the carbon atom). Is sometimes referred to as "carbon atom (A)"), and the peak observed in the range of 171 to 176 ppm is an aliphatic group of carbon atoms of the carbonyl group of the ester bond of the polyester polyol.
  • carbon atom (B) It is a peak assigned to a carbon atom of a carbonyl group (hereinafter, the carbon atom may be referred to as "carbon atom (B)") which is directly bonded to a carbon atom constituting the group.
  • the carbon atom (A) can be, for example, a carbon atom represented by the following formula (1)
  • the carbon atom (B) can be, for example, a carbon atom represented by the following formula (2).
  • the integral value of the peak attributed to the carbon atom of the carbonyl group of the ester bond of the structural unit derived from the polyester polyol (corresponding to the above (C (A) + C (B))) is assigned to the carbon atom (A).
  • C (A) / (C (A) + C (B)) in the above formula (X) is the carbon atom (A) with respect to the sum of the total amount of carbon atoms (A) and the total amount of carbon atoms (B). It means the ratio of the total amount of carbon atoms (the sum of the total amount of carbon atoms (A) / the total amount of carbon atoms (A) and the total amount of carbon atoms (B)).
  • the polyester polyol can be a polycondensation reaction product of a polyhydric alcohol and a polycarboxylic acid.
  • the carbon atom (A) and the carbon atom (B) are carbon atoms derived from a polycarboxylic acid.
  • the carbon atom (A) is a carbon atom of a carbonyl group (of the carboxylic acid) that is directly bonded to the carbon atom constituting the aromatic ring among the carbon atoms derived from the polycarboxylic acid.
  • the carbon atom (B) is a carbon atom of a carbonyl group (of a carboxylic acid) that is directly bonded to a carbon atom constituting an aliphatic group among carbon atoms derived from polycarboxylic acid.
  • C (A) / (C (A) + C (B)) in the formula (X) is mainly derived from the type, content, and polycarboxylic acid of the polycarboxylic acid constituting the structural unit derived from the polyester polyol. It tends to be possible to adjust by changing the type, content, etc. of the polyester polyol to be produced.
  • C (A) and C (C) have the following formula (Y), where C (C) is the integral value of the peaks observed in the range of 150 to 155 ppm in 13 C-NMR analysis. It may be satisfied. 3.6 ⁇ C (A) / C (C) (Y)
  • the peak observed in the range of 160 to 180 ppm is mainly the carbon atom of the carbonyl group of the urethane bond formed by the reaction between the polyol of the urethane prepolymer and the polyisocyanate (hereinafter, the carbon).
  • the atom is sometimes referred to as a "carbon atom (C)").
  • the carbon atom (C) can be, for example, a carbon atom represented by the following formula (3).
  • C (A) / C (C) in the above formula (Y) is the ratio of the total amount of carbon atoms (A) to the total amount of carbon atoms (C) (total amount of carbon atoms (A) / carbon atom (C). Total amount).
  • C (A) / C (C) The larger C (A) / C (C), the larger the ratio of carbon atoms (A) per carbon atom (C) in the urethane prepolymer (that is, the aroma contained in the polyester polyol per urethane bond). It can be said that the ratio of rings is large).
  • C (A) / C (C) in the formula (Y) is a structural unit mainly derived from a polyester polyol, like C (A) / (C (A) + C (B)) in the formula (X). It tends to be possible to adjust by changing the type and content of the polycarboxylic acid constituting the above, the type and content of the polyester polyol derived from the polycarboxylic acid, and the like.
  • the reactive hot melt adhesive contains a urethane prepolymer having a polymer chain containing a structural unit derived from a polyol and a structural unit derived from polyisocyanate, and an isocyanate group bonded to the end of the polymer chain.
  • a urethane prepolymer having a polymer chain containing a structural unit derived from a polyol and a structural unit derived from polyisocyanate, and an isocyanate group bonded to the end of the polymer chain.
  • C (A) integral value of the peak observed in the range of 163 to 170 ppm
  • C (C) and C (C) satisfy the following formula (Y).
  • Such a reactive hot melt adhesive has excellent adhesive strength and elasticity.
  • the structural unit derived from the polyol may include a structural unit derived from a polyester polyol having an aromatic ring.
  • the reactive hot melt adhesive may be used to bond a plurality of adherends selected from cloth and paper to each other.
  • the combination of the adherends may be cloth and cloth, paper and paper, or cloth and paper.
  • the present disclosure further applies the above urethane prepolymer-containing composition as a reactive hot melt adhesive used to bond a plurality of adherends selected from cloth and paper to each other, or cloth. And applications for the manufacture of reactive hot melt adhesives used to bond a plurality of adherends selected from paper to each other.
  • the adhesive body includes a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other.
  • the adhesive layer contains a cured product of the above reactive hot melt adhesive.
  • the garment includes the above-mentioned adhesive body, and the first adherend and the second adherend may be cloth.
  • the garment may be non-sewn garment.
  • the method for producing the adhesive includes a step of forming an adhesive layer by melting the above-mentioned reactive hot melt adhesive and applying it to a first adherend, and a second coating on the adhesive layer. It includes a step of arranging the adherends and crimping the second adherend to obtain a laminate, and a step of curing the adhesive layer in the laminate to obtain an adhesive.
  • a reactive hot melt adhesive having excellent adhesive strength and excellent elasticity is provided. Further, according to the present disclosure, there is provided an adhesive using such a reactive hot melt adhesive and a method for producing the same. Further, according to the present disclosure, garments provided with an adhesive are provided.
  • FIG. 1 is a schematic view showing a method for manufacturing an adhesive according to an embodiment
  • FIGS. 1 (a), (b), (c), and (d) are schematic views showing each step.
  • FIG. 2 is a 13 C-NMR spectrum of the urethane prepolymer B of Production Example 2 in the range of 150 to 180 ppm.
  • FIG. 3 is a 13 C-NMR spectrum of the urethane prepolymer E of Production Example 5 in the range of 150 to 180 ppm.
  • polyol means a compound having two or more hydroxy groups in the molecule.
  • polyisocyanate means a compound having two or more isocyanate groups in the molecule.
  • amorphous polyester polyol means a polyester polyol having a melting point (Tm)
  • crystalline polyester polyol means a polyester polyol having a melting point (Tm).
  • the reactive hot melt adhesive of one embodiment contains a urethane prepolymer.
  • a reactive hot melt adhesive is capable of exhibiting adhesive strength and the like by increasing the molecular weight by a chemical reaction.
  • the urethane prepolymer having an isocyanate group cures (forms a cured product) by reacting with moisture, the urethane prepolymer alone can act as a reactive hot melt adhesive, but the reactive hot melt adhesive can be used.
  • the agent may contain a component other than the urethane prepolymer.
  • the urethane prepolymer may be, for example, a urethane prepolymer having an isocyanate group.
  • a urethane prepolymer having an isocyanate group usually has a polymer chain containing a structural unit derived from a polyol and a structural unit derived from polyisocyanate, and an isocyanate group.
  • the isocyanate group may be bonded to the end of the polymerized chain.
  • the structural unit derived from the polyol may include a structural unit derived from the polyester polyol.
  • a urethane prepolymer having a structural unit derived from a polyester polyol can usually be obtained by reacting a polyol containing a polyester polyol with a polyisocyanate. That is, the urethane prepolymer may be a reaction product of a polyol containing a polyester polyol and a polyisocyanate. The content of the constituent unit can be adjusted by changing the mixing ratio of the polyester polyol giving the constituent unit and the polyol other than the polyester polyol giving the constituent unit. Further, since a urethane bond is formed by the reaction of the polyol and the polyisocyanate, the polymerized chain of the urethane prepolymer may have a urethane bond. Further, by increasing the equivalent of polyisocyanate with respect to the equivalent of polyol, an isocyanate group can be introduced at the end of the polymerized chain.
  • C (A) / (C (A) + C (B)) is the ratio of the total amount of carbon atoms (A) to the sum of the total amount of carbon atoms (A) and the total amount of carbon atoms (B) (carbon atoms (A)). ) / The sum of the total amount of carbon atoms (A) and the total amount of carbon atoms (B)).
  • the larger C (A) / (C (A) + C (B)) the larger the proportion of carbon atom (A) in the structural unit derived from the polyester polyol constituting the urethane prepolymer (that is, it is contained in the polyester polyol). It can be said that the proportion of aromatic rings is large).
  • C (A) / (C (A) + C (B)) is 0.36 or more, and may be 0.38 or more, or 0.40 or more.
  • C (A) / (C (A) + C (B)) is 0.36 or more, the reactive hot melt adhesive tends to have excellent adhesive strength and excellent elasticity.
  • the upper limit of C (A) / (C (A) + C (B)) is 1.00 or less, 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less because it is superior in adhesive strength. , 0.75 or less, 0.70 or less, 0.65 or less, or 0.60 or less.
  • C (A) and C (C) have the following formula (Y), where C (C) is the integral value of the peaks observed in the range of 150 to 155 ppm in 13 C-NMR analysis. It may be satisfied. 3.6 ⁇ C (A) / C (C) (Y)
  • C (A) / C (C) means the ratio of the total amount of carbon atoms (A) to the total amount of carbon atoms (C) (total amount of carbon atoms (A) / total amount of carbon atoms (C)).
  • C (A) / C (C) may be 3.6 or more, and may be 3.8 or more or 4.0 or more.
  • the reactive hot melt adhesive tends to be more excellent in adhesive strength and more excellent in elasticity.
  • the upper limit of C (A) / C (C) may be 10 or less, 8 or less, 7 or less, 6.5 or less, or 6 or less because the adhesive strength is more excellent.
  • C (A) / (C (A) + C (B)) in the formula (X) and C (A) / C (C) in the formula (Y) mainly constitute a structural unit derived from a polyester polyol. It tends to be possible to adjust by changing the type and content of the polycarboxylic acid, the type and content of the polyester polyol derived from the polycarboxylic acid, and the like.
  • the type, content, and the like of the structural unit derived from the polyol are not particularly limited as long as the urethane prepolymer satisfies the formula (X) and further the formula (Y).
  • the urethane prepolymer when the ratio of the structural unit derived from the polyol to the structural unit derived from the polyester polyol having an aromatic ring is large, the urethane prepolymer easily satisfies the formulas (X) and (Y). I found that there was a tendency.
  • the polyol and polyisocyanate constituting the urethane prepolymer will be described by taking the urethane prepolymer containing such a structural unit as an example.
  • Component (a) Polyol
  • the structural unit derived from the component (a) may be referred to as a polyester polyol having an aromatic ring (hereinafter, “component (a1))”. ) Is included.
  • the structural unit derived from the component (a) may further include a structural unit derived from a polyol other than the polyester polyol having an aromatic ring (hereinafter, may be referred to as “component (a2)”).
  • the polyester polyol having an aromatic ring may be a crystalline polyester polyol having a melting point (Tm) or an amorphous polyester polyol having no melting point (Tm), but is an amorphous polyester polyol. May be.
  • the component (a1) may be a polycondensation reaction product of a polyhydric alcohol and a polycarboxylic acid.
  • the component (a1) may be a linear polyester diol formed from a diol and a dicarboxylic acid, or a branched polyester triol formed from a triol and a dicarboxylic acid.
  • the branched polyester triol can also be obtained by reacting a diol with a tricarboxylic acid.
  • polyhydric alcohol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol isomers, pentandiol isomers, hexanediol isomers, and 2,2-.
  • Aromatic or alicyclic diols such as diols, 1,4-cyclohexanedimethanol; aromatic diols such as 4,4'-dihydroxydiphenylpropane, bisphenol A, bisphenol F, pyrocatechol, resorcinol, hydroquinone (having an aromatic ring). Diol) and the like.
  • One type of polyhydric alcohol may be used alone, or two or more types may be used in combination. Among these, an aliphatic diol is preferable, and an aliphatic diol having 2 to 6 carbon atoms is more preferable.
  • the carbon atom of the carbonyl group (of the carboxylic acid) such as phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid is directly bonded to the carbon atom constituting the aromatic ring.
  • Polycarboxylic acid hereinafter, may be referred to as "aromatic polycarboxylic acid”); maleic acid, fumaric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, malonic acid, succinic acid.
  • Examples thereof include polycarboxylic acids in which atoms are directly bonded to carbon atoms constituting an aliphatic group (hereinafter, may be referred to as "aliphatic polycarboxylic acid” in some cases).
  • the aromatic polycarboxylic acid may be a polycarboxylic acid in which the carbon atom of the carbonyl group (of the carboxylic acid) is directly bonded to the carbon atom constituting the benzene ring, and consists of phthalic acid, isophthalic acid, and terephthalic acid. It may be at least one selected from the group.
  • One type of polycarboxylic acid may be used alone, or two or more types may be used in combination.
  • the adjustment of C (A) / (C (A) + C (B)) in the formula (X) and C (A) / C (C) in the formula (Y) is to adjust the ratio of the aromatic polycarboxylic acid. Can be done by.
  • a polycarboxylic acid derivative such as a carboxylic acid anhydride or a compound in which a part of the carboxyl group is esterified can also be used.
  • the polycarboxylic acid derivative include phthalic anhydride, dimethyl terephthalate, dodecylmaleic acid, octadecenylmaleic acid and the like.
  • the component (a1) may be a polycondensation reaction product of a polyhydric alcohol and a polycarboxylic acid containing an aromatic polycarboxylic acid.
  • the content of the constituent unit derived from the aromatic polycarboxylic acid) is the total amount of the constituent units constituting the component (a1) (polycondensation reaction product). As a reference, it may be, for example, 10 to 60 mol%.
  • the content of the structural unit derived from the compound having an aromatic ring may be 15 mol% or more or 20 mol% or more, 55 mol% or less, or 55 mol% or less, based on the total amount of the structural units constituting the component (a1). It may be 50 mol% or less.
  • a polycarboxylic acid in which the component (a1) contains a polyvalent alcohol and an aromatic polycarboxylic acid a polycarboxylic acid having an aromatic ring, preferably at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.
  • the content of the structural unit derived from the aromatic polycarboxylic acid is 20 to 100 mol% and 25 to 100 mol% based on the total amount of the structural unit derived from the polycarboxylic acid. , Or 30-100 mol%.
  • the number average molecular weight (Mn) of the component (a1) may be 500 to 12000 from the viewpoint of adhesive strength.
  • the number average molecular weight (Mn) of the component (a1) may be 1000 or more, 1500 or more, or 1800 or more, or 11000 or less, 10000 or less, or 9000 or less.
  • Mn is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
  • the measurement of GPC for obtaining the number average molecular weight (Mn) can be performed under the following conditions, for example.
  • the content of the component (a1) (constituent unit derived from the component (a1)) is 50% by mass or more, 55% by mass or more, based on the total amount of the component (a) (constituent unit derived from the component (a)). It may be 60% by mass or more, 65% by mass or more, 70% by mass or more, or 75% by mass or more.
  • the content of the component (a1) is 50% by mass or more based on the total amount of the component (a)
  • the obtained urethane prepolymer tends to have excellent initial adhesive strength.
  • the upper limit of the content of the component (a1) is based on the total amount of the component (a) (constituent unit derived from the component (a)) from the viewpoint of workability. It may be 100% by mass or less, 95% by mass or less, or 90% by mass or less.
  • the total amount of the component (a) (constituent unit derived from the component (a)) is used. When it is 100 mol%, it may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more, and 100 mol% or less, 95 mol% or more. It may be less than or equal to 90 mol% or less.
  • the component (a2) is a polyol other than the polyester polyol having an aromatic ring.
  • Examples of the component (a2) include polyester polyols having no aromatic ring, polyether polyols, polyether ester polyols, polyurethane polyols, polycarbonate polyols, and polyolefin polyols.
  • the component (a) may contain a polyether polyol having an aromatic ring as the component (a2) from the viewpoint of improving the initial adhesive strength.
  • the polyether polyol having an aromatic ring may be an amorphous polyether polyol.
  • the polyether polyol having an aromatic ring may be a polyether polyol having a bisphenol skeleton, and the bisphenol skeleton may be a bisphenol A skeleton or a bisphenol F skeleton.
  • the polyether polyol having a bisphenol A skeleton or a bisphenol F skeleton may be a bisphenol A or bisphenol F modified with an alkylene oxide, and more specifically, a bisphenol A or a propylene oxide modified. May be good.
  • the component (a) tends to be more excellent in adhesive strength by containing the polyether polyol having such a bisphenol skeleton as the component (a2).
  • the content of the polyether polyol having a bisphenol skeleton may be 0 to 10% by mass, based on the total amount of the component (a) (the structural unit derived from the component (a)), and may be 1% by mass or more and 2% by mass. It may be more than or equal to 3% by mass or more, and may be 8% by mass or less, 6% by mass or less, or 5% by mass or less.
  • the content of the polyether polyol having an aromatic ring having a bisphenol skeleton may be 0 to 10 mol% when the total amount of the component (a) (the structural unit derived from the component (a)) is 100 mol%. It may be 1 mol% or more, 2 mol% or more, or 3 mol% or more, and may be 8 mol% or less, 6 mol% or less, or 5 mol% or less.
  • the number average molecular weight (Mn) of the component (a2) may be 100 to 10000 from the viewpoint of reducing the viscosity of the urethane prepolymer.
  • the number average molecular weight (Mn) of the component (a2) may be 400 or more or 1000 or more, and may be 8000 or less or 5000 or less.
  • Mn is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
  • the content of the component (a2) may be 0 to 50% by mass based on the total amount of the component (a) (constituent unit derived from the component (a)). It may be 5% by mass or more or 10% by mass or more, and may be 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.
  • the content of the component (a2) (constituent unit derived from the component (a2)) is 0 to 50 mol% when the total amount of the component (a) (constituent unit derived from the component (a)) is 100 mol%. It may be 5 mol% or more, 10 mol% or more, 45 mol% or less, 40 mol% or less, 35 mol% or less, 30 mol% or less, or 25 mol% or less.
  • Polyisocyanate can be used without particular limitation as long as it is a compound having two or more isocyanate groups.
  • the polyisocyanate may be a compound having two isocyanate groups (diisocyanate).
  • examples of the polyisocyanate include aromatic isocyanates such as diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylenediisocyanate; and dicyclohexylmethane diisocyanate and isophorone diisocyanate.
  • Alicyclic isocyanate examples thereof include aliphatic isocyanates such as hexamethylene diisocyanate.
  • the polyisocyanate preferably contains an aromatic diisocyanate, and more preferably contains a diphenylmethane diisocyanate.
  • One type of polyisocyanate may be used alone, or two or more types may be used in combination.
  • the urethane prepolymer can be synthesized by reacting the component (a) containing the component (a1) at a predetermined content with the component (b).
  • the urethane prepolymer is bonded to a polymer chain containing a structural unit derived from the component (a1) and a structural unit derived from the component (b) at the end of the polymer chain. It has an isocyanate group.
  • the equivalent ratio of the isocyanate group (NCO) of the component (b) to the hydroxy group (OH) of the component (a) (the isocyanate group (NCO) equivalent of the component (b) / (a) )
  • Component hydroxy group (OH) equivalent, NCO / OH) may be 1.1 or more, and may be 1.1 to 2.1.
  • NCO / OH is 1.1 or more
  • the urethane prepolymer has an isocyanate group bonded to the end of the polymerized chain, and it is possible to suppress an increase in the viscosity of the urethane prepolymer, further improving workability. There is a tendency.
  • foaming is less likely to occur during the moisture curing reaction of the reactive hot melt adhesive, and it tends to be easy to suppress a decrease in adhesive strength.
  • the temperature and time for reacting the component (a) and the component (b) when synthesizing the urethane prepolymer are not particularly limited, but may be, for example, 85 to 120 ° C. and 0.1 minutes to 48 hours.
  • the urethane prepolymer may satisfy both the following condition (i) and condition (ii).
  • Such a reactive hot melt adhesive containing a urethane prepolymer is excellent in initial adhesive strength and excellent in workability.
  • the melt viscosity of the urethane prepolymer at 120 ° C. is 1 to 30 Pa ⁇ s.
  • the melt viscosity at 120 ° C. may be 3 Pa ⁇ s or more, 5 Pa ⁇ s or more, 7 Pa ⁇ s or more, or 10 Pa ⁇ s or more, 28 Pa ⁇ s or less, 25 Pa ⁇ s or less, 20 Pa ⁇ s or less, or 15 Pa ⁇ s or less.
  • -It may be s or less.
  • the melt viscosity of the urethane prepolymer at 80 ° C. is 100 Pa ⁇ s or more.
  • the melt viscosity of the urethane prepolymer at 80 ° C. is 100 Pa ⁇ s or more, the viscosity required for the adhesive force is developed at an early stage, and as a result, the initial adhesive force is excellent.
  • the melt viscosity at 80 ° C. may be 110 Pa ⁇ s or more, 120 Pa ⁇ s or more, 130 Pa ⁇ s or more, or 140 Pa ⁇ s or more.
  • melt viscosity at 120 ° C. is measured by a rotary rheometer device.
  • the melt viscosity at 120 ° C. and the melt viscosity at 80 ° C. of the urethane prepolymer are measured by a rotary rheometer device, and are measured by, for example, the following methods.
  • a separate sample for measuring the melt viscosity at 120 ° C. and a sample for measuring the melt viscosity at 80 ° C. are prepared and measured.
  • the measuring device and measuring conditions are as follows.
  • Rotary rheometer device DHR-2 (TA Instruments Japan Co., Ltd.) ⁇ Geometry: ⁇ 20mm (2 °) cone plate ⁇ GAP: 57 ⁇ m ⁇ Shear velocity: 33 (1 / s) -Melting viscosity at 120 ° C: Measured value measured after incubating urethane prepolymer (reactive hot melt adhesive) at 120 ° C for 5 minutes-Melting viscosity at 80 ° C: Urethane prepolymer (reactive hot melt adhesive) Measured after keeping the temperature at 80 ° C for 5 minutes
  • the melt viscosity of the urethane prepolymer can be adjusted mainly by changing the type, content, etc. of the structural unit derived from the polyol.
  • the type, content, and the like of the structural unit derived from the polyol are not particularly limited as long as the urethane prepolymer satisfies the condition (i) and the condition (ii).
  • the urethane prepolymer when the structural unit derived from the polyol contains the structural unit derived from the polyester polyol having an aromatic ring, the urethane prepolymer easily satisfies the condition (i) and the condition (ii). It has been found that the urethane prepolymer which tends to satisfy the condition (i) and the condition (ii) tends to satisfy the formulas (X) and (Y) easily.
  • the reactive hot melt adhesive may further contain a catalyst from the viewpoint of accelerating the curing of the urethane prepolymer and developing higher adhesive strength.
  • a catalyst from the viewpoint of accelerating the curing of the urethane prepolymer and developing higher adhesive strength.
  • the catalyst include dibutyltin dilaurate, dibutylthione octate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, dimorpholinodiethyl ether (bis (2-morpholinoethyl) ether) and the like.
  • the content of the catalyst may be 0.001 to 0.5% by mass based on the total amount of the reactive hot melt adhesive.
  • the reactive hot melt adhesive may further contain a thermoplastic polymer from the viewpoint of increasing the rubber elasticity of the adhesive layer to be formed and further improving the impact resistance.
  • thermoplastic polymer examples include polyurethane, ethylene-based copolymer, propylene-based copolymer, vinyl chloride-based copolymer, acrylic copolymer, and styrene-conjugated diene block copolymer.
  • the content of the thermoplastic polymer may be 0.1 to 50% by mass based on the total amount of the reactive hot melt adhesive.
  • the reactive hot melt adhesive may further contain a tackifier resin from the viewpoint of imparting a stronger adhesive force to the formed adhesive layer.
  • a tackifier resin examples include rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, petroleum resin, hydrogenated petroleum resin, kumaron resin, ketone resin, and styrene resin. Examples thereof include modified styrene resin, xylene resin, and epoxy resin.
  • the content of the tackifier resin may be 0.1 to 50% by mass based on the total amount of the reactive hot melt adhesive.
  • the reactive hot melt adhesive may further contain other components, if necessary.
  • other components include antioxidants, pigments, ultraviolet absorbers, surfactants, flame retardants, fillers, photocolorants, thermal color inhibitors, fragrances, imaging agents, thermal cross-linking agents and the like.
  • the content of the other components may be 0.001 to 10% by mass based on the total amount of the reactive hot melt adhesive.
  • the reactive hot melt adhesive may consist of urethane prepolymer alone or may contain other components in addition to urethane prepolymer.
  • the reactive hot melt adhesive consists of urethane prepolymer alone, if the urethane prepolymer satisfies both the conditions (i) and (ii), the reactive hot melt adhesive also satisfies the conditions (i) and condition (ii). Satisfy both. Further, even when the reactive hot melt adhesive contains other components in addition to the urethane prepolymer, by containing the urethane prepolymer that satisfies both the condition (i) and the condition (ii).
  • a reactive hot-melt adhesive having excellent initial adhesive strength and excellent workability, and the reactive hot-melt adhesive can satisfy both the condition (i) and the condition (ii). Further, even if the reactive hot melt adhesive containing an arbitrary urethane prepolymer and other components satisfies both the condition (i) and the condition (ii), the initial adhesive strength is excellent and the workability is excellent. Can be excellent.
  • the reactive hot melt adhesive may satisfy both the following condition (i) and condition (ii).
  • the reactive hot melt adhesive may contain a urethane prepolymer.
  • the preferred ranges of the melt viscosity at 120 ° C. and the melt viscosity at 80 ° C. of the reactive hot melt adhesive are the same as the preferable ranges of the melt viscosity at 120 ° C. and the melt viscosity at 80 ° C. of the above urethane prepolymer. Further, the measurement conditions for the melt viscosity of the reactive hot melt adhesive are the same as the measurement conditions for the melt viscosity of the urethane prepolymer. Therefore, a duplicate description will be omitted here.
  • the content of the urethane prepolymer based on the total amount of the reactive hot melt adhesive is 80% by mass or more, 85% by mass or more, 90% by mass or more, 92% by mass or more, 95% by mass or more, or 97% by mass. % Or more, and may be 100% by mass.
  • melt viscosity of the urethane prepolymer satisfies both the condition (i) and the condition (ii)
  • melt viscosity of the reactive hot melt adhesive also easily satisfies both the condition (i) and the condition (ii). ..
  • the temperature is 23 ° C. and 50% because the isocyanate group of the urethane prepolymer contained in the reactive hot melt adhesive reacts with the moisture in the air or the moisture on the surface of the adherend. It can be cured by leaving (curing) at RH (relative humidity) for 24 hours. In this way, a cured product of the reactive hot melt adhesive can be obtained.
  • the reactive hot melt adhesive can be used, for example, by melting at 60 to 130 ° C. and then applying it to an adherend.
  • the coating method is not particularly limited, and examples thereof include a method using a coating device such as a bar coater, a die coater, a roll coater, and a spray. When applying to a narrow part such as a small part, a dispenser is suitable.
  • the application pattern of the reactive hot melt adhesive can be appropriately set, and examples thereof include a dot-like, linear, zigzag-like, planar, and curved application patterns.
  • the reactive hot melt adhesive can adhere various adherends via a cured product (adhesive layer) of the reactive hot melt adhesive.
  • the adherend include metal base materials such as SUS and aluminum, and non-metal base materials such as cloth, paper, polycarbonate, polyamide, polyetherimide, glass, and carbon fiber.
  • the adherend may be, for example, cloth or paper.
  • Reactive hot melt adhesives can be suitably used to bond a plurality of adherends selected from cloth and paper to each other.
  • the combination of adherends can be cloth and cloth, paper and paper, or cloth and paper.
  • the reactive hot melt adhesive can be suitably used for clothing such as clothing (apparel products), supporters, bags, wallets, interiors, various covers, cases, wearable devices, etc., and can be particularly preferably used for clothing. ..
  • the reactive hot melt adhesive may be formed in the form of a film and used as an adhesive film.
  • Such an adhesive film is obtained by applying, for example, a reactive hot melt adhesive onto a support film such as a PET (polyethylene terephthalate) film to form an adhesive layer to obtain an adhesive film. Can be done.
  • the thickness of the adhesive layer (adhesive film) may be 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more, and may be 300 ⁇ m or less, 250 ⁇ m or less, or 200 ⁇ m or less. The thicker the film, the more the adhesive strength tends to be secured, and the thinner the film, the easier it is to secure the elasticity.
  • the adhesive body of one embodiment includes a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other.
  • the adhesive layer contains a cured product of the above reactive hot melt adhesive. Examples of the article provided with the adhesive include clothing (particularly, non-sewn clothing), semiconductor devices, electronic devices, and the like.
  • the first adherend and the second adherend may be, for example, cloth or paper, and the combination of the first adherend and the second adherend may be cloth and cloth, paper and paper. Alternatively, it may be cloth and paper. When the article provided with the adhesive is clothing, the first adherend and the second adherend are cloth.
  • the adhesive of the present embodiment has a step of melting the above-mentioned reactive hot melt adhesive and applying it to a first adherend to form an adhesive layer, and a second adherend on the adhesive layer.
  • the temperature at which the reactive hot melt adhesive is melted may be, for example, 60 to 130 ° C.
  • Examples of the method of applying the reactive hot melt adhesive to the first adherend include a method of using a coating device such as a die coater, a roll coater, or a spray. When applying to a narrow part such as a small part, a dispenser is suitable.
  • Examples of the method of crimping the second adherend include a method of crimping using a pressure roll or the like.
  • the reactive hot melt adhesive in the adhesive layer can be cured by, for example, leaving (curing) at a temperature of 23 ° C. and 50% RH (relative humidity) for 24 hours. Thereby, the adhesive layer may contain a cured product of the reactive hot melt adhesive.
  • FIG. 1 is a schematic view showing a method for manufacturing an adhesive according to an embodiment
  • FIGS. 1 (a), (b), (c), and (d) are schematic views showing each step.
  • a method for manufacturing an adhesive using a stretchable cloth, which is a cloth, as the first adherend and the second adherend will be described.
  • the elastic fabric 1 is installed along the jig 10 (see (a) in FIG. 1).
  • the reactive hot melt adhesive of the present embodiment is applied to a predetermined portion of the stretchable fabric 1 to form the adhesive layer 4 (see FIG. 1 (b)).
  • the material and shape of the jig 10 are not particularly limited, and can be appropriately selected depending on the intended purpose.
  • the application of the reactive hot melt adhesive may be carried out using, for example, a dispenser.
  • the elastic fabric 2 is arranged on the adhesive layer 4, and the elastic fabric 1 and the elastic fabric 2 are passed through the adhesive layer 4 while applying pressure from above the elastic fabric 2 by a roll or the like. To obtain a laminated body 20 (see (c) and (d) of FIG. 1).
  • the reactive hot melt adhesive in the adhesive layer 4 is moisture-cured, and an adhesive body in which the elastic fabrics are adhered to each other can be obtained.
  • the adhesive layer 4 in the adhesive contains a cured product of the reactive hot melt adhesive.
  • an adhesive film made of a reactive hot melt adhesive previously formed on a releasable substrate is transferred onto the elastic fabric 1 to form an adhesive layer 4.
  • You may.
  • an adhesive may be provided on the stretchable fabric 2 and bonded to the stretchable fabric 1.
  • the garment of one embodiment comprises the above-mentioned adhesive.
  • the first adherend and the second adherend may be cloth.
  • the garment can be non-sewn garment.
  • the urethane prepolymer contained in the reactive hot melt adhesive of the present embodiment can identify the constituent components of the urethane prepolymer by, for example, solution NMR measurement.
  • the reactive hot melt adhesive of the present embodiment contains a component other than the urethane prepolymer, for example, the urethane prepolymer is isolated by preparative liquid chromatography (known means such as GPC), and the solvent is retained.
  • the components of the urethane prepolymer can be identified by performing solution NMR measurement after the removal. Further, by using the same method, components other than the urethane prepolymer contained in the reactive hot melt adhesive can be specified.
  • the uncured component of the reactive hot melt adhesive of the present embodiment for example, only the uncured component is extracted using a solvent in which the uncured component of the cured product such as tetrahydrofuran is dissolved and the cured product itself is difficult to dissolve.
  • a solvent in which the uncured component of the cured product such as tetrahydrofuran is dissolved and the cured product itself is difficult to dissolve By decomposing the undissolved component (cured product component) of the residue with pyridine and breaking the urethane bond, the constituent components of the urethane prepolymer before curing can be specified.
  • urethane prepolymers A to E of Production Examples 1 to 5 were prepared using the polyols and polyisocyanates of the types and parts by mass shown in Table 1. More specifically, Table 1 shows the equivalent ratio ((NCO) equivalent / (OH) equivalent) of the isocyanate group of the polyisocyanate to the hydroxy group of the polyol with respect to the polyol previously dehydrated by the vacuum dryer. The mixture was added to the reaction vessel so as to have the values shown, and mixed at 110 ° C. for 1 hour until uniform.
  • the urethane prepolymer was obtained by further defoaming and stirring at 110 ° C. for 1 hour under reduced pressure.
  • the obtained urethane prepolymer has a polymer chain containing a structural unit derived from a polyol and a structural unit derived from a polyisocyanate. It is presumed to have an isocyanate group bonded to the end of the polymerized chain.
  • the obtained urethane prepolymer was used as it was as a reactive hot melt adhesive.
  • Polyester (a1) Polyester polyol having an aromatic ring (a1) -1: Non-polyester having an aromatic ring containing dicarboxylic acid (adipic acid and isophthalic acid) and diol (ethylene glycol and neopentyl glycol) as main components.
  • Crystalline polyester polyol (number of hydroxyl groups: 2, number average molecular weight: 2000, content of structural units derived from a compound having an aromatic ring: 25 mol% (based on the total amount of structural units constituting the amorphous polyester polyol), 50 mol % (Based on the total amount of constituent units derived from dicarboxylic acid), melting point (Tm): none)
  • A1 -2 Acrystalline polyester polyol having an aromatic ring containing a dicarboxylic acid (phthalic anhydride) and a diol (ethylene glycol and diethylene glycol) as main components (number of hydroxyl groups: 2, number average molecular weight: 2000, aromatic) Content of constituent units derived from a ring-bearing compound: 50 mol% (based on the total amount of constituent units constituting the amorphous polyester polyol), 100 mol% (based on the total amount of constituent units derived from dicarboxylic acid), melting point (Tm) ):none)
  • Polyesters other than (a2) and (a1) (a2) -1 Acyclic having no aromatic ring and containing dicarboxylic acid (adipic acid) and diol (1,4-butanediol and neopentyl glycol) as main components.
  • Polyester polyol (number of hydroxyl groups: 2, number average molecular weight: 5000, melting point (Tm): none)
  • A2) -3 Achromatic polyether polyol having an aromatic ring (bisphenol A / PO system) (manufactured by ADEKA Corporation, trade name: BPX-11, number of hydroxyl groups: 2, melting point (Tm): none)
  • 13 C-NMR analysis was performed on urethane prepolymers A to E. 13 C-NMR analysis was carried out using AVANCE NEO (probe: CryoProbe TM ) manufactured by Bruker Japan Co., Ltd. as a nuclear magnetic resonance spectrometer (NMR) under the following measurement conditions.
  • AVANCE NEO probe: CryoProbe TM
  • NMR nuclear magnetic resonance spectrometer
  • FIG. 2 is a 13 C-NMR spectrum of the urethane prepolymer B of Production Example 2 in the range of 150 to 180 ppm.
  • the integrated value (C (B)) of the peak observed in the range of 171 to 176 ppm is 10.000, the integrated value of the peak observed in the range of 163 to 170 ppm.
  • the integral values (C (C)) of (C (A)) and the peaks observed in the range of 150 to 155 ppm were 33.039 and 5.081, respectively.
  • FIG. 3 is a 13 C-NMR spectrum of the urethane prepolymer E of Production Example 5 in the range of 150 to 180 ppm.
  • Example 1 to 3 and Comparative Examples 1 and 2 ⁇ Evaluation of reactive hot melt adhesive> -Initial Adhesive Strength and Final Adhesive Strength
  • the reactive hot-melt adhesives (urethane prepolymers A to E) of Examples 1 to 3 and Comparative Examples 1 and 2 are melted at 120 ° C. and stretchable fabrics (spandex, Toray Op).
  • An adhesive layer was formed by applying it on Lycra (registered trademark) manufactured by Rontex Co., Ltd. and applying it to a thickness of 80 ⁇ m with a bar coater. The same elastic fabric was placed on the formed adhesive layer and crimped at 120 ° C. to obtain a crimped body.
  • the adhesive strength of the crimped body after 5 minutes from the time of crimping was measured using a force gauge (manufactured by Imada Co., Ltd., DS250N), and this was used as the initial adhesive strength of the reactive hot melt adhesive.
  • the pressure-bonded body was cured in a constant temperature bath at 23 ° C. and 50% RH for 1 day, and the adhesive layer was cured to prepare an adhesive body.
  • the adhesive strength of the adhesive is measured by a T-type peel strength test using a tensile tester (manufactured by Shimadzu Corporation, EZ-Test EZ-SX) at a measurement temperature of 25 ° C and a tensile speed of 100 mm / min. This was used as the final adhesive strength.
  • Table 1 The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif thermofusible réactif qui contient un prépolymère d'uréthane. Lorsque C(A) est la valeur intégrale du pic observé à 163-170 ppm pendant l'analyse par RMN 13C du prépolymère d'uréthane, et C(B) est la valeur intégrale du pic observé à 171-176 ppm, C(A) et C(B) satisfont l'expression (X).　(X) 0,36≤C(A)/(C(A)+C(B)).
PCT/JP2020/014927 2020-03-31 2020-03-31 Adhésif thermofusible réactif, corps lié et son procédé de production, et vêtement WO2021199339A1 (fr)

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JP2022511403A JPWO2021199339A1 (fr) 2020-03-31 2020-03-31
PCT/JP2020/014927 WO2021199339A1 (fr) 2020-03-31 2020-03-31 Adhésif thermofusible réactif, corps lié et son procédé de production, et vêtement
CN202080099156.3A CN115335568A (zh) 2020-03-31 2020-03-31 反应性热熔黏合剂、黏合体及其制造方法以及衣物

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JP2021161218A (ja) * 2020-03-31 2021-10-11 昭和電工マテリアルズ株式会社 反応性ホットメルト接着剤、接着体及びその製造方法、並びに衣類

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JPH0635386A (ja) * 1992-07-22 1994-02-10 Bando Chem Ind Ltd 電子写真複写機用クリーニングブレードの製法
JP2001026762A (ja) * 1999-07-13 2001-01-30 Toyobo Co Ltd 反応性ホットメルト接着剤及びそれを用いた接着芯地
JP2008530308A (ja) * 2005-02-11 2008-08-07 インヴィスタ テクノロジー エスアエルエル 無溶媒の水性ポリウレタン分散液およびそれからの造形品
JP4147571B2 (ja) * 2001-10-31 2008-09-10 日本ポリウレタン工業株式会社 布地用反応性ホットメルト接着剤及び布地の接着方法
WO2016045074A1 (fr) * 2014-09-26 2016-03-31 Henkel (China) Investment Co. Ltd. Adhésif thermofusible réactif à base de polyuréthanne et son utilisation

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Publication number Priority date Publication date Assignee Title
JPH0635386A (ja) * 1992-07-22 1994-02-10 Bando Chem Ind Ltd 電子写真複写機用クリーニングブレードの製法
JP2001026762A (ja) * 1999-07-13 2001-01-30 Toyobo Co Ltd 反応性ホットメルト接着剤及びそれを用いた接着芯地
JP4147571B2 (ja) * 2001-10-31 2008-09-10 日本ポリウレタン工業株式会社 布地用反応性ホットメルト接着剤及び布地の接着方法
JP2008530308A (ja) * 2005-02-11 2008-08-07 インヴィスタ テクノロジー エスアエルエル 無溶媒の水性ポリウレタン分散液およびそれからの造形品
WO2016045074A1 (fr) * 2014-09-26 2016-03-31 Henkel (China) Investment Co. Ltd. Adhésif thermofusible réactif à base de polyuréthanne et son utilisation

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Publication number Priority date Publication date Assignee Title
JP2021161218A (ja) * 2020-03-31 2021-10-11 昭和電工マテリアルズ株式会社 反応性ホットメルト接着剤、接着体及びその製造方法、並びに衣類
JP7516815B2 (ja) 2020-03-31 2024-07-17 株式会社レゾナック 反応性ホットメルト接着剤、接着体及びその製造方法、並びに衣類

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